|Publication number||US6642402 B2|
|Application number||US 10/178,014|
|Publication date||Nov 4, 2003|
|Filing date||Jun 21, 2002|
|Priority date||Apr 30, 2001|
|Also published as||CA2445856A1, CA2445856C, EP1390375A1, EP1390375A4, EP1390375B1, US20030045737, WO2002088153A1|
|Publication number||10178014, 178014, US 6642402 B2, US 6642402B2, US-B2-6642402, US6642402 B2, US6642402B2|
|Inventors||Karin A. Voll Barclay, Jeffrey M. Sullivan, Dawn A. Arkin, Fredric R. Askham|
|Original Assignee||Boulder Scientific Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (6), Referenced by (2), Classifications (8), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part of U.S. patent application Ser. No. 09/938,952 filed Aug. 24, 2001 now abandoned, which in turn is a continuation-in-part of U.S. patent application Ser. No. 09/845,627 filed Apr. 30, 2001 now abandoned.
This invention relates to bis(cyclopentadienyl) and bis(indenyl) ruthenium complexes which are useful in chemical vapor deposition (CV) and other procedures.
The state of the art relevant to this invention as of Jul. 17, 1997 is summarized in U.S. Pat. No. 6,002,036. A process for the synthesis of bis(alkylcyclopentadienyl) ruthenium complexes by treatment of RuCl3 hydrates and ethylcyclopentadiene or isopropylcyclopentadiene with zinc powder in an alcohol solvent at −30° C. to 0° C. is described.
The invention comprises synthesis of bis(cyclopentadienyl), bis(alkylcyclopentadienyl), bis(indenyl) or bis(alkylindenyl) liquid and solid ruthenium complexes by treating ruthenium trichloride hydrate and a cyclopentadienyl compound or an indenyl compound with magnesium powder in C2 to C8 alkanol, e.g., ethanol. The treating may be accomplished at a temperature from about 10° C. to about −30° C.
As used in this specification, the following terms have the meaning set forth:
(1) Cyclopentadienyl Compound
A compound of the formula
in which each R is independently hydrogen or a C1 to C10 alkyl group. C1 to C5 monoalkyl cyclopentadienyl compounds are preferred.
(2) Indenyl Compound
A compound of formula
in which each R is independently hydrogen or a C1 to C10 alkyl group. C1 to C5 monoindenyl compounds are preferred.
Ruthenium trichloride dihydrate, a cyclopentadienyl or indenyl compound, and an alkanol, preferably ethanol, are combined and treated with magnesium powder of about minus 100 (−100) to 200 mesh at low temperatures with an appropriate stir out. A bis(cyclopentadienyl) or bis(indenyl) ruthenocene may be isolated by filtration, followed by combination with an aliphatic or aromatic hydrocarbon solvent, preferably hexane or toluene, another filtration, and subsequent passage through a silica column. Final products, if solids, may be isolated in >99% purity in yields of about 65 weight percent by crystallization from a hydrocarbon solvent. High purity liquid products may be isolated by fractional distillation.
Ruthenium trichloride dihydrate is dissolved in ethanol. The solution is cooled to −20 C. to −30° C. and 4.0 to 4.4 equivalents of ethylcyclopentadiene (EtCp) are added. Over the course of 1 hr to 1.5 hr, magnesium powder (minus 100 mesh) (3.0 equivalents) is added as the pot temperature is maintained at −10° C. to −30° C. The consequent reaction mixture is stirred out for about 19 hours at 10-15° C., or until gas chromatography analysis indicates that the reaction is complete. Thereafter, the reaction mixture is filtered, and the ethanol and unreacted ethyl cyclopentadiene are removed under vacuum. Nexane and 3.0 equivalents of Na2SO4 are added to the remaining slurry which is then stirred for 1-20 hrs. The solids are removed by filtration through Celite. The remaining yellow solution is distilled under vacuum to an oil. The yellow oil can be isolated in >99% purity with yields of 65%. Hexane is added back to the oil, followed by a filtration through Celite® or silica. A final run through a silica column may be appropriate to remove any color bodies.
Hexane is stripped from the yellow solution so produced. Pentane is added to the residual oil, and the product, (EtCp)2Ru, is crystallized at −30° C. After removal of the supernatant, the pentane is then pumped off under vacuum. More than one crystallization may be appropriate to enhance purity. This synthesis is illustrated by equation 1:
Any cyclopentadienyl or any indenyl compound as defined herein may be substituted for ethylcyclopentadiene in Example 1.
Magnesium powder of any desired mesh size, preferably minus 100 (−100) to 200 mesh, may be used. Any C2 to C8 alkanol may be used instead of ethanol.
Alternatively, a preformed alkanol solution of ruthenium trichloride dihydrate may be added to a preformed slurry of magnesium powder and alkyl cyclopentadiene at a temperature of about 0° C. to
A magnesium slurry was produced by adding 45.62 g of minus 100 (−100) mesh magnesium powder (made by READE) (1.88 moles, 3 equivalents) slowly to a 5 liter vessel containing 1.2L of ethanol (Filmex) at room temperature (25° C.). 323.00 g of 76.8% pure cyclopentadiene (3.75 moles) at a temperature of about −50° C. was added to the magnesium slurry, which was at room temperature, through an addition funnel. To this, a 0.35M solution of RuCl3*1.8H2O in ethanol (Filmex) (0.625 moles in 1.8L of ethanol) was added over a 2.5 hour time period, via addition funnel, between −10° C. and 10° C. The slurry turned sequentially from a grey color to brown to green to blue, and then back to grey/brown as each addition of ruthenium trichloride was made. The mixture was then stirred at a temperature of from 5° C. to 10° C. for 3 hours, and was then stirred out to room temperature overnight. The ethanol was then distilled off under rough pump, and about three to four liters of toluene was added back. The distillation was switched from rough pump to atmospheric pressure and was continued until a pot temperature of 110° C. was reached. The yellow solution was hot filtered (100° C.) through a cake of Celite® that had been washed with hot toluene (100° C.). The filtrate was concentrated by distillation until the yellow solution reached a volume of 650 mL. The yellow product crystallized out of the toluene solution as it cooled to room temperature. The yellow slurry was further cooled in a dry ice/acetone bath, and the light yellow crystalline solids were filtered on to a Buchner funnel, washed with 100 mL of hexane, and pumped dry giving 134.3 g of ruthenocene (93% yield from first crop).
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US6002036 *||Mar 8, 1999||Dec 14, 1999||Kabushikikaisha Kojundokagaku Kenkyusho||Process for producing bis(alkyl-cyclopentadienyl)ruthenium complexes and process for producing ruthenium-containing films by using the same|
|US6521772 *||Sep 27, 2001||Feb 18, 2003||Praxair Technology, Inc.||Synthesis of substituted ruthenocene complexes|
|US20020058106 *||Aug 8, 2001||May 16, 2002||Tanaka Kikinzoku Kogyo K.K.||Process for preparing a bis (alkylcyclopentadienyl) ruthenium, bis (alkylcyclopentadienyl) ruthenium prepared thereby, and chemical vapor deposition of a ruthenium film or ruthenium-compound film|
|US20020064948 *||Mar 13, 2001||May 30, 2002||Tanaka Kikinzoku Kogyo K.K. (Japanese Corporatin)||Preparation method of bis (alkylcyclopentadienyl) ruthenium|
|US20020065427 *||Sep 24, 2001||May 30, 2002||Tanaka Kikinozoku Kogyo K.K.||Organometallic compounds for chemical vapor deposition and their preparing processes, and processes for chemical vapor deposition of precious-metal films and precious-metal compound films|
|US20020103395 *||Nov 8, 2001||Aug 1, 2002||Tanaka Kikinzoku Kogyo K.K.||Method of producing bis (cyclopentadienyl) ruthenium derivative, bis (cyclopentadienyl) ruthenium derivative produced by the same method, and method of producing thin film of ruthenium or ruthenium compound|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US7893290||Apr 13, 2010||Feb 22, 2011||W.C. Heraeus Gmbh||Process for the preparation of bis(pentadienyl)-complexes of iron group metals|
|EP2383277A1||Jun 16, 2010||Nov 2, 2011||Heraeus Precious Metals GmbH & Co. KG||Process for the preparation of bis (pentadienyl)-complexes of iron group metals|
|U.S. Classification||556/136, 427/252|
|International Classification||C07B61/00, C07F15/00, C07F17/00, C07F17/02|
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